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Precise Synthesis of High Generation Dendrimer-Like Star-Branched Polymers and Their Applications

高世代树枝状星形支化聚合物的精密合成及其应用

基本信息

批准号：
18350060
负责人：
HIRAO Akira
金额：
$ 10.91万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2006
资助国家：
日本
起止时间：
2006 至 2007
项目状态：
已结题

项目摘要

Dendrimer-like star-branched polymers have been synthesized by developing a novel methodology which involves two basic reactions: (1) linking reaction of α-functionalized living anionic polymers with benzyl bromide-functionalized polymers and (2) transformation reaction to benzyl bromides. The two reactions proceeded quantitatively several times, resulting in the formation of high-generation dendrimer-like star-branched polymers up to seventh generation. The resulting polymer (7th generation) is a really huge macromolecule possessing two million in molecular weight and a narrow molecular weight distribution (Mw/Mn =1.02) and comprising 508 polymer segments with 512 termini. Highly dense polymers consisting of four branches at each junction have also succeeded in synthesizing the polymers up to the third generation. The attempt to synthesize the 4th generation polymer was not successful possibly due to the steric hindrance. Other functional polymer segments have been successfully introduced into the outermost layers of dendrimer-like star-branched polymers. They involve poly(2-vinylpyridine), poly(tert-butyl methacrylate), poly(3-perfluorobutylpropyl methacrylate), and poly(2,3-dihydroxypropyl methacrylate), respectively. By introducing such segments, basic, acidic, ionic, hydrophobic and lipophobic, water-soluble characters could be provided to the polymers. Furthermore, the introduction of methacrylate polymers having liquid crystalline, chirality, and thermoresponsive characters were also successful. Their functional polymers have been examined in detail with respect to such functionalities. The shapes of the dendrimer-like star-branched polymers have been measured by SAXS and found to be ellipsoidal shapes rather than spherical ones. AFM structural imaging of the dendrimer-like star-branched polymers has been realized. The structures based on synthetic methodology as well as internal branching points could be clearly observed for the first time.

通过两个基本反应合成了树枝状星形支化聚合物：（1）α-功能化活性阴离子聚合物与苄基溴功能化聚合物的连接反应和（2）苄基溴的转化反应。这两个反应进行了几次定量，导致高世代的树枝状星形支化聚合物的形成高达第七代。得到的聚合物（第7代）是具有200万分子量和窄分子量分布（Mw/Mn =1.02）的真正巨大的大分子，并且包含508个具有512个末端的聚合物链段。在每个连接处由四个分支组成的高密度聚合物也成功地合成了第三代聚合物。合成第四代聚合物的尝试没有成功，可能是由于空间位阻。其他功能性聚合物链段已成功地引入到树枝状星形支化聚合物的最外层中。它们分别涉及聚（2-乙烯基吡啶）、聚（甲基丙烯酸叔丁酯）、聚（甲基丙烯酸3-全氟丁基丙酯）和聚（甲基丙烯酸2，3-二羟丙酯）。通过引入这样的链段，可以向聚合物提供碱性、酸性、离子性、疏水性和疏脂性以及水溶性特征。此外，还成功地引入了具有液晶性、手性和温敏特性的甲基丙烯酸酯聚合物。它们的功能聚合物已被详细检查相对于这样的功能。用小角X射线散射（SAXS）测量了树枝状星形支化聚合物的形状，发现它们是椭球形而不是球形。实现了树状星形支化聚合物的AFM结构成像。基于合成方法学的结构以及内部分支点首次可以清楚地观察到。